CN103979497B - A kind of method preparing high-purity hydrochloric acid - Google Patents
A kind of method preparing high-purity hydrochloric acid Download PDFInfo
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- CN103979497B CN103979497B CN201410207482.8A CN201410207482A CN103979497B CN 103979497 B CN103979497 B CN 103979497B CN 201410207482 A CN201410207482 A CN 201410207482A CN 103979497 B CN103979497 B CN 103979497B
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 238000000034 method Methods 0.000 title claims description 22
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012498 ultrapure water Substances 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000009835 boiling Methods 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 15
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000012856 packing Methods 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 6
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 5
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000443 aerosol Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 31
- 238000004821 distillation Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 20
- 229910021645 metal ion Inorganic materials 0.000 description 17
- 239000011347 resin Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 239000002585 base Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- -1 after oxidation Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000306 recurrent effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is open from the purified industrial method preparing ultra-clean and high pure chemical reagent grade hydrochloric acid of technical-grade hydrochloric acid, technical hydrochloric acid is filtered, after activated carbon fiber dechlorination, after anion-exchange resin column carries out ion-exchange, heating evaporation, after gas phase fraction removes high boiling substance by the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, gas phase fraction enters stannous sulfate solution and washs, after high purity water washing, high purity water absorbs, obtain high-purity hydrochloric acid product, second distillation can also be comprised, reach high-quality, efficiently, the object of industrialized mass production ultra-clean and high pure chemical reagent hydrochloric acid.
Description
Technical field
The present invention relates to the manufacture method of reagent grade hydrochloric acid, specifically from the purified industrial method preparing ultra-clean and high pure chemical reagent grade hydrochloric acid of technical-grade hydrochloric acid.
Background technology
Ultra-clean and high pure chemical reagent (Ultra-cleanandHigh-purityReagents) is called process chemical (ProcessChemicals) in the world, it is one of key basic chemical industry material in unicircuit (IC) and super large-scale integration (VLSI) making processes, be mainly used in the cleaning of chip, etching, ultra-clean and high pure chemical reagent also adulterates for chip in addition and the cleaning on depositing technology and silicon wafer surface.The purity of ultra-clean and high pure chemical reagent and cleanliness factor all have very important impact to the yield rate of unicircuit, electrical property and reliability.The main application fields of ultra-clean and high pure chemical reagent comprises semicon industry and sun power industry and precision components and makes, and semicon industry ultra-clean and high pure chemical reagent requires relatively high, and current China high-end product mainly relies on import, domestic main production mid and low-end products.
Semiconductor equipment and material structure (SEMI) have set up SEMI chemical reagent standard committee in 1975, the international standard of tailor ultra-clean and high pure chemical reagent.Ultra-clean and high pure chemical reagent is divided into 4 grades by range of application by current international SEMI standardization body: (1) SEMI-C1 standard (being applicable to the making of >1.2 μm of IC Technology); (2) SEMI-C7 standard (being suitable for the making of 0.8-1.2 μm of IC Technologies); (3) SEMI-C8 standard (being applicable to the making of 0.2-0.6 μm of IC Technology); (4) SEMI-C12 standard (being applicable to the making of 0.09-0.2 μm of IC Technology).
The production method of purification of current ultra-clean and high pure chemical reagent hydrochloric acid is a lot, have isothermal diffusion process, distillation method, method boiled in Asia, rectification method, ion exchange adsorption, gas assimilating method etc., boil in Asia in clean environment (or boiling in two Asia), and method of purification effect is best, and product purity is also the highest.Sub-boiling distillation is a kind of very effective means removing metal ion and solia particle in liquid, the key of this technology be exactly by the liquid heat that is purified to lower than boiling point with 5 ~ 20 DEG C.Because liquid does not reach boiling point, and the gas phase of liquid equilibrium is also just no longer made up of a large amount of steam thing grain, but with molecularity and liquid equilibrium, therefore seldom carries secretly in steam or do not carry metal ion and solia particle secretly.But sub-boiling distillation exists the high deficiency of the industrial production cost that yields poorly, especially to the sub-boiling distillation of volatile products, because its tower reactor liquid phase temperature rate of change is comparatively large, cause temperature control to regulate frequent, cause the stability of technological operation to decline.The high-purity hydrochloric acid that single metal ion is less than 0.1ppb will be produced in addition, use technical-grade hydrochloric acid is raw material, single sub-boiling distillation cannot meet the specification of quality that single metal ion is less than the high-purity hydrochloric acid of 0.1ppb, industrialized sub-boiling distillation can not save the initial processing steps to raw material hydrochloric acid, still needs the multistage purifying process taking distillation → physical or chemical treatment → gas absorption → sub-boiling distillation.
CN102923660A discloses a kind of preparation method of reagent hydrochloric acid, the technical hydrochloric acid of HCl >=36.5% is diluted, successively through plastic resin treatment, charcoal absorption process, add tin protochloride mixing after distillation, collect cut obtain reagent hydrochloric acid.Plastic resin treatment utilizes most metal chloride in concentrated hydrochloric acid easily to form the characteristic of network cl anion, as Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+anion complex is generated: Me in hydrochloric acid
n++ xCl
-=MeCl
x -(X – n), use anionite-exchange resin by MeCl
x -(X – n)adsorption
,but Ca
2+, Mg
2+, Na
+, Sr
2+, Ba
2+meCl can not be formed in alkali and alkaline earth metal ions ion
x -(X – n)and can not remove; Charcoal absorption is utilized to dissociate Cl and organic substance; Utilize SnCl
2reductibility process further free Cl, reduction Fe
3+, As
3+.There are three deficiencies in the method: one is that anionite-exchange resin can be oxidized by free Cl in technical hydrochloric acid, after oxidation, resin can come off and chain rupture by generating portion group, produce rudimentary amine and enter into hydrochloric acid soln, cause the pollution to hydrochloric acid, and negative resin exchange capacity is declined, shorten its work-ing life; Two is the SnCl added
2finally stay in dilute hydrochloric acid, the large concentration of volume is low, reclaims more difficult; Three is SnCl
2the not adsorbable Ca of anionite-exchange resin can not be removed
2+, Ba
2+, Sr
2+plasma.
Summary of the invention
Object of the present invention, for above technical problem, proposes a kind of method efficiently preparing high-purity hydrochloric acid.
Concrete technical scheme of the present invention is as follows: filtered by the micro-strainer of technical hydrochloric acid by 0.45 μm of aperture, after flowing through activated carbon fiber dechlorination, enter anion-exchange resin column and carry out ion-exchange, heater heats is evaporated, control vapor pressure is 0.1 ~ 0.15MPa, after gas phase fraction removes high boiling substance by the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, enter the first gas-fog separator and isolate liquid phase, particulate and gas phase fraction, gas phase fraction enters 20 ~ 50 DEG C, the stannous sulfate solution of weight concentration 10 ~ 20% washs, after the high purity water washing of 10 ~ 20 DEG C, enter the second gas-fog separator again and carry out aerosol separation, the gas phase fraction high purity water of 10 ~ 15 DEG C absorbs, when absorption liquid density d
15during=1.185 ~ 1.194g/ml, obtain SEMI-C8 level high-purity hydrochloric acid product.
For improving the purity of hydrochloric acid further, second distillation can also be comprised, the SEMI-C8 level high-purity hydrochloric acid product obtained is joined in rectifying tower, thread high purity quartz is added as filler in the tower joint of rectifying tower, heating kettle heating makes hydrochloric acid boiling rectifying, and controlling reflux ratio is 3 ~ 6 ︰ 1, and the gas phase fraction of tower top is after condensation, filter with the micro-strainer in 0.1 μm of aperture, become SEMI-C12 level high-purity hydrochloric acid product.
In the present invention, micro-strainer preferably uses the micro-filter of ultrapure tetrafluoroethylene material, guarantees that preparation process does not occur pollutent.
Activated carbon fiber preferably uses cellulose base activated carbon fiber, following pre-treatment is carried out: cellulose base activated carbon fiber boiled after washing 1 ~ 10 hour in pure water before using, soak 8 ~ 20 hours with the mixed organic solvents of the volume ratio of ethanol, methyl alcohol or Yi Bing Chun ︰ acetone=4 ~ 6 ︰ 1,3 ~ 10 hours are washed boiling again with the hydrochloric acid of 1 ~ 5wt%, then boil with the sodium hydroxide of 1 ~ 5wt% and wash 3 ~ 10 hours, finally with pure water in immersion, boil and be washed till washing water in neutral, be dried to constant weight at 100 ~ 120 DEG C.Free Cl can be adsorbed and reduce to activated carbon fiber after treatment, free Cl concentration can drop to 0.05 ~ 0.1ppm, its rate of adsorption is 10 ~ 100 times of gac, and loading capacity is 5 ~ 10 times of gac, except go back adsorb organic compound matter, part heavy metal ion.
Anionite-exchange resin adopts strong-basicity styrene series anion resin, as 201 × 7 strongly basic anionic resins, can exchange Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+anion complex Me is generated in hydrochloric acid
n++ xCl
-=MeCl
x -(X – n), removing Zn
2+, Fe
3+, Cu
2+, Co
2+, Mn
2+deng metal ion.
Well heater preferably makes the heat exchanger obtained with the following method: by the ultrapure tetrafluoroethylene of graphite impregnation melting or after flooding ultrapure polytetrafluoroethylsolution solution, and being linked by tetrafluoroethylene shapingly becomes interchanger.
The graphite packing of flooding ultrapure tetrafluoroethylene is that graphite is embedded in tetrafluoroethylene by graphite impregnation at the ultrapure tetrafluoroethylene of melting or the particulate material that formed after being immersed in ultrapure polytetrafluoroethylsolution solution.
Can also moderate amount of sulfuric acid be contained in above-mentioned stannous sulfate solution, as the sulfuric acid of 1 ~ 10wt%, become the sub-solution of tin of acid sulfuric acid, be more conducive to Ca
2+, Ba
2+, Sr
2+isoionic precipitation, and stannous sulfate hydrolytic precipitation can be prevented.
Instant invention overcomes the shortcoming and defect of sub-boiling distillation and current prior art, reach the object of high-quality, efficient, industrialized mass production ultra-clean and high pure chemical reagent hydrochloric acid.Compared with prior art, tool has the following advantages in the present invention:
1, pretreated cellulose base carbon fiber adsorption and catalytic combustion is adopted and the free Cl of reduction, free Cl can drop to 0.05 ~ 0.1ppm, remove the free Cl of in raw material hydrochloric acid (liquid phase) more than 99.8%, and reduce free Cl to the oxidation of anionite-exchange resin, reduce anionite-exchange resin oxidation products to the pollution of hydrochloric acid, extend the work-ing life of anionite-exchange resin.
2, gas phase fraction through 10 ~ 20% stannous sulfate solution wash after, free Cl, Fe remaining in reducible removing gas phase hydrochloric acid
3+, As
3+, the not adsorbable Ca of anionite-exchange resin can also be removed with the form of vitriol precipitation
2+, Ba
2+, Sr
2+plasma.Collaborative, complementary, the synergy that serve negative resin Adsorption metal ion act on.Stannous sulfate strength of solution is high, volume is little, therefore makes the recovery of pink salt become easy.
3, the graphite packing tower of the ultrapure tetrafluoroethylene of dipping is used, the efficient gas-fog separator of two-stage carries out gas-liquid separation, remove or reduce metal ion, solia particle that gas phase hydrochloric acid is carried secretly, both ensure that rectifying had higher gas speed, serve again Asia and to boil the effect of rectifying.High-purity hydrochloric acid product single metal ion after a rectifying drops to 0.5 ~ 1ppb respectively, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, close to or meet SEMI-C12 standard-required.
4, in the tower joint of rectifying tower, thread high purity quartz is added as filler, it is made to possess good aerosol centrifugation, reduce metal ion to be taken out of by steam, improve the high and product purity of separation efficiency, after secondary rectifying, product quality indicator is more than SEMI-C12 standard simultaneously.
Accompanying drawing explanation
Fig. 1 is the equipment schematic diagram of preparation process in one embodiment of the present invention and use.
The device name that number in the figure is corresponding: the ultrapure tetrafluoroethylene micro-strainer in 0.45 μm, 1-aperture; 2-pure quartz glass heat exchanger package; 3-activated carbon fiber post; 4-anion-exchange resin column; 5-flood the graphite heater of ultrapure tetrafluoroethylene; 6-flood the graphite heater of ultrapure tetrafluoroethylene; 7-flood the graphite packing stripping tower of ultrapure tetrafluoroethylene; 8-be incubated efficient first gas-fog separator (liner is ultrapure tetrafluoroethylene); 9-stannous sulfate washing tank (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is the tube bank of ultrapure tetrafluoroethylene); 10-high purity water washing tank (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is the tube bank of ultrapure tetrafluoroethylene); 11-high purity water tourie (liner is ultrapure tetrafluoroethylene, and built-in heat exchanger tube side is the tube bank of ultrapure tetrafluoroethylene); 12-be incubated efficient second gas-fog separator (liner is ultrapure tetrafluoroethylene); 13-Venturi spray tube (liner is ultrapure tetrafluoroethylene); 14-pure quartz glass spinner-type flowmeter (ultrapure tetrafluoroethylene rotor); 15-liner is the pump of ultrapure tetrafluoroethylene; The ultrapure tetrafluoroethylene micro-strainer in 0.22 μm, 16-aperture; 17-middle product storage tank (liner is ultrapure tetrafluoroethylene); 18-high-purity thread quartz filler rectifying tower group; 19-ultra-clean and high pure chemical reagent hydrochloric acid tank (liner is ultrapure tetrafluoroethylene); The ultrapure tetrafluoroethylene micro-strainer in 0.1 μm, 20-aperture.
Embodiment
Pre-treatment before cellulose base activated carbon fiber uses: first boil with pure water and wash 6 hours, with the water-soluble impurity of stripping last traces; By the mixed organic solvents soaking at room temperature 12 hours of the ethanol of volume ratio 5 ︰ 1 and acetone, with the absorption property of Activation Activity Carbon fibe and the residual organic substance of removing, organic solvent takes low temperature, vacuum analysis method to reclaim; Boil with the hydrochloric acid of 3wt% again and wash 6 hours, with the caustic solubility impurity of stripping last traces; Then boil with the aqueous sodium hydroxide solution of 3wt% and wash 6 hours, with the acid soluble impurities of stripping last traces; Finally with pure water immersion, boil be washed till washing water in neutral only, and be dried to constant weight at 110 DEG C.
Embodiment 1:
A, pre-treatment and a rectifying:
(single metal ion content is about 1 ~ 80ppm to technical hydrochloric acid by 36.5% respectively, free Cl concentration is 60ppm) the ultrapure tetrafluoroethylene micro-strainer 1 that continues through 0.45 μm, aperture with the speed of 500L/h filters, pure quartz glass heat exchanger package 2 tentatively heats, the dechlorination of pretreated cellulose base activated carbon fiber post 3, after 201 × 7 strongly basic anionic resin post 4 ion-exchanges, adopt the graphite heater 5 of the high-purity tetrafluoroethylene of dipping, 6 heating evaporations, control vapor pressure is about 0.12Mpa, after gas phase fraction removes high boiling substance (stripping rectifying) by the graphite packing tower 7 of the ultrapure tetrafluoroethylene of dipping, enter efficient first gas-fog separator 8 of insulation and remove droplet and particulate.Gas phase fraction enters the chemical treatment of B step.
Liquid fraction is a dilute hydrochloric acid of 20.4 ~ 21.5%, mixes, after realizing energy reuse, be directly used in the rectifying of general reagent hydrochloric acid without cooling with technical hydrochloric acid.
Carry out middle control inspection to the hydrochloric acid by cellulose base activated carbon fiber post 3, free Cl drops to 0.08ppm, and carry out middle control inspection to the gas phase hydrochloric acid after stripping rectifying, single metal ion drops to 10 ~ 40ppb respectively.
B, chemical treatment and pure water and absorption:
The acid stannous sulfate aqueous solution containing 5wt% sulfuric acid and 10wt% stannous sulfate is added in washing tank 9, a certain amount of high purity water (resistivity 18.3 Ω cm) is added respectively in high purity water washing tank 10, high purity water tourie 11, unlatching liner is that the pump 15 of ultrapure tetrafluoroethylene makes the liquid in high purity water tourie 11 be in recurrent state, and the size of its flow is regulated by pure quartz glass spinner-type flowmeter 14.
The gas phase fraction removing droplet and particulate in the first gas-fog separator 8 washs respectively by washing tank 9 chemical subtraction, high purity water washing tank 10, be incubated after efficient second gas-fog separator 12 removes droplet and particulate, be extracted in high purity water tourie 11 by the negative pressure (-0.01 ~-0.04MPa) that Venturi spray tube 13 produces, cyclic absorption becomes product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid.
In the middle of ultra-clean and high pure chemical reagent hydrochloric acid in product preparation process, the temperature of the stannous sulfate chemical pretreatment solution in washing tank 9 controls between 25 ~ 50 DEG C, and should regularly replace, and relief liquor is used for remanufacture technical grade stannic oxide.High purity water washings temperature in high purity water washing tank 10 controls at 15 ~ 20 DEG C, when its density d
20during=1.155 ~ 1.158g/ml, (content of hydrochloric acid: 31.14 ~ 32.00%) puts it into common high purity reagent hydrochloric acid tank, and changes high purity water.
High purity water absorption liquid temperature in high purity water tourie 11 controls at 10 ~ 15 DEG C, when its density d
15during=1.185 ~ 1.194g/ml (content of hydrochloric acid 36.31 ~ 38.00wt%), after being filtered by 0.22 μm of ultrapure tetrafluoroethylene micro-strainer 16, pump into middle product storage tank 17 by pump 15.
In hydrochloric acid warp in middle product storage tank 17, control detects, single metal ion drops to 0.5 ~ 1ppb respectively, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, close to or meet SEMI-C12 standard-required, can be used as SEMI-C8 standard-required hydrochloric acid product use.
C, secondary rectifying:
By product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid with 300L/h, join in rectifying tower group continuously, thread high purity quartz is added as filler in the tower joint of rectifying tower group 18, when the volume of hydrochloric acid in heating kettle is 30 ~ 50% of heating kettle volume, start to carry out electrically heated rectifying, control gas phase fraction and condensing reflux weight ratio are 4 ︰ 1.The size of reflux ratio takes over a business temperature and the flow of water coolant in tubular type reflux exchanger by control tower, regulate the opening degree of quantity of reflux variable valve, or the hold-time of electromagnetism pendulum opening and closing realizes.
After the gas phase fraction condensing cooling on after-fractionating tower top, enter ultra-clean and high pure chemical reagent hydrochloric acid tank 19, control its density d
15=1.190 ~ 1.194g/ml, through the ultra-clean filtration of 0.1 μm of ultrapure tetrafluoroethylene micro-strainer 20, ultra-clean packing can obtain single metal ion and be less than 0.05 ~ 0.1ppb, and content is the ultra-clean and high pure chemical reagent hydrochloric acid of 37.5%, its assay is in table 1, and quality index is more than SEMI-C12 standard.
The liquid fraction of after-fractionating tower still is the secondary dilute hydrochloric acid of 20 ~ 21%, directly enters pure quartz glass heat exchanger package 2, by the thermal exchange with primary industry hydrochloric acid, realize energy reuse without cooling.The secondary dilute hydrochloric acid of 20 ~ 21% is used for 5NNH
4the preparation of the Cl aqueous solution.
Embodiment 2:
A, pre-treatment and a rectifying:
(single metal ion content is about 1 ~ 80ppm to technical hydrochloric acid by 31% respectively, free Cl concentration is 50ppm) the ultrapure tetrafluoroethylene micro-strainer 1 that continues through 0.45 μm, aperture with the speed of 500L/h filters, pure quartz glass heat exchanger package 2 tentatively heats, the dechlorination of pretreated cellulose base activated carbon fiber post 3, after 201 × 7 strongly basic anionic resin post 4 ion-exchanges, adopt the graphite heater 5 of the high-purity tetrafluoroethylene of dipping, 6 heating evaporations, control vapor pressure is about 0.15Mpa, after gas phase fraction removes high boiling substance (stripping rectifying) by the graphite packing tower 7 of the ultrapure tetrafluoroethylene of dipping, enter efficient first gas-fog separator 8 of insulation and remove droplet and particulate.Gas phase fraction enters the chemical treatment of B step.
Liquid fraction is a dilute hydrochloric acid of 20.4 ~ 21.5%, mixes, after realizing energy reuse, be directly used in the rectifying of general reagent hydrochloric acid without cooling with technical hydrochloric acid.
Through checking by control in the hydrochloric acid of cellulose base activated carbon fiber post 3, free Cl drops to 0.08ppm, and carry out middle control inspection to the gas phase hydrochloric acid after stripping rectifying, single metal ion drops to 10 ~ 40ppb respectively.
B, chemical treatment and pure water and absorption:
The acid stannous sulfate aqueous solution containing 5wt% sulfuric acid and 15wt% stannous sulfate is added in washing tank 9, a certain amount of high purity water (resistivity 18.3 Ω cm) is added respectively in high purity water washing tank 10, high purity water tourie 11, unlatching liner is that the pump 15 of ultrapure tetrafluoroethylene makes the liquid in high purity water tourie 11 be in recurrent state, and the size of its flow is regulated by pure quartz glass spinner-type flowmeter 14.
The gas phase fraction removing droplet and particulate in the first gas-fog separator 8 washs respectively by washing tank 9 chemical subtraction, high purity water washing tank 10, be incubated after efficient second gas-fog separator 12 removes droplet and particulate, be extracted in high purity water tourie 11 by the negative pressure (-0.01 ~-0.04MPa) that Venturi spray tube 13 produces, cyclic absorption becomes product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid.
In the middle of ultra-clean and high pure chemical reagent hydrochloric acid in product preparation process, the temperature of the stannous sulfate chemical pretreatment solution in washing tank 9 controls between 25 ~ 50 DEG C, and should regularly replace, and relief liquor is used for remanufacture technical grade stannic oxide.High purity water washings temperature in high purity water washing tank 10 controls at 15 ~ 20 DEG C, when its density d
20during=1.155 ~ 1.158g/ml, (content of hydrochloric acid: 31.14 ~ 32.00%) puts it into common high purity reagent hydrochloric acid tank, and changes high purity water.
High purity water absorption liquid temperature in high purity water tourie 11 controls at 10 ~ 15 DEG C, when its density d
15during=1.185 ~ 1.194g/ml (content of hydrochloric acid 36.31 ~ 38.00wt%), after being filtered by 0.22 μm of ultrapure tetrafluoroethylene micro-strainer 16, pump into middle product storage tank 17 by pump 15.
In hydrochloric acid warp in middle product storage tank 17, control detects, single metal ion drops to 0.5 ~ 1ppb respectively, and free Cl does not detect, and exceeds the specification of quality of SEMI-C8 grade standard, close to or meet SEMI-C12 standard-required, can be used as SEMI-C8 standard-required hydrochloric acid product use.
C, secondary rectifying:
By product in the middle of ultra-clean and high pure chemical reagent hydrochloric acid with 300L/h, join in rectifying tower group continuously, thread high purity quartz is added as filler in the tower joint of rectifying tower group 18, when the volume of hydrochloric acid in heating kettle is 30 ~ 50% of heating kettle volume, start to carry out electrically heated rectifying, control gas phase fraction and condensing reflux weight ratio are 5 ︰ 1.The size of reflux ratio takes over a business temperature and the flow of water coolant in tubular type reflux exchanger by control tower, regulate the opening degree of quantity of reflux variable valve, or the hold-time of electromagnetism pendulum opening and closing realizes.
After the gas phase fraction condensing cooling on after-fractionating tower top, enter ultra-clean and high pure chemical reagent hydrochloric acid tank 19, control its density d
15=1.190 ~ 1.194g/ml, through the ultra-clean filtration of 0.1 μm of ultrapure tetrafluoroethylene micro-strainer 20, ultra-clean packing can obtain single metal ion and be less than 0.05 ~ 0.1ppb, and content is the ultra-clean and high pure chemical reagent hydrochloric acid of 37.5%, its assay is in table 2, and quality index is more than SEMI-C12 standard.
The liquid fraction of after-fractionating tower still is the secondary dilute hydrochloric acid of 20 ~ 21%, directly enters pure quartz glass heat exchanger package 2, by the thermal exchange with primary industry hydrochloric acid, realize energy reuse without cooling.The secondary dilute hydrochloric acid of 20 ~ 21% is used for 5NNH
4the preparation of the Cl aqueous solution.
Table 1:
Table 2:
Claims (6)
1. prepare the method for high-purity hydrochloric acid for one kind, it is characterized in that, the micro-strainer of technical hydrochloric acid by 0.45 μm of aperture is filtered, after flowing through activated carbon fiber dechlorination, enter anion-exchange resin column and carry out ion-exchange, heater heats is evaporated, control vapor pressure is 0.1 ~ 0.15MPa, after gas phase fraction removes high boiling substance by the graphite packing tower of the ultrapure tetrafluoroethylene of dipping, enter the first gas-fog separator and isolate liquid phase, particulate and gas phase fraction, gas phase fraction enters 20 ~ 50 DEG C, the stannous sulfate solution of weight concentration 10 ~ 20% washs, after the high purity water washing of 10 ~ 20 DEG C, enter the second gas-fog separator again and carry out aerosol separation, the gas phase fraction high purity water of 10 ~ 15 DEG C absorbs, when absorption liquid density d
15during=1.185 ~ 1.194g/ml, obtain SEMI-C8 level high-purity hydrochloric acid product.
2. prepare the method for high-purity hydrochloric acid according to claim 1, it is characterized in that, also comprise secondary rectifying, the SEMI-C8 level high-purity hydrochloric acid product obtained is joined in rectifying tower, thread high purity quartz is added as filler in the tower joint of rectifying tower, heating kettle heating makes hydrochloric acid boiling rectifying, control gas phase fraction and condensing reflux weight ratio are 3 ~ 6 ︰ 1, the gas phase fraction of tower top is after condensation, filter with the micro-strainer in 0.1 μm of aperture, become SEMI-C12 level high-purity hydrochloric acid product.
3. according to claim 1 or 2, prepare the method for high-purity hydrochloric acid, it is characterized in that, described activated carbon fiber carries out following pre-treatment before using: activated carbon fiber boiled after washing 1 ~ 10 hour in pure water, the mixed organic solvents formed by the volume ratio of ethanol, methyl alcohol or Yi Bing Chun ︰ acetone=4 ~ 6 ︰ 1 soaks 8 ~ 20 hours, 3 ~ 10 hours are washed boiling again with the hydrochloric acid of 1 ~ 5wt%, then boil with the sodium hydroxide of 1 ~ 5wt% and wash 3 ~ 10 hours, finally with pure water in immersion, boil and be washed till washing water in neutral, be dried to constant weight at 100 ~ 120 DEG C.
4. prepare the method for high-purity hydrochloric acid according to claim 3, it is characterized in that, described activated carbon fiber is cellulose base activated carbon fiber.
5. according to claim 1 or 2, prepare the method for high-purity hydrochloric acid, it is characterized in that, described well heater is by after the tetrafluoroethylene of graphite impregnation melting or dipping polytetrafluoroethylsolution solution, links shaping heat exchanger by tetrafluoroethylene.
6. according to claim 1 or 2, prepare the method for high-purity hydrochloric acid, it is characterized in that, the sulfuric acid also containing 1-10wt% in described stannous sulfate solution.
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| WO2017080113A1 (en) | 2015-11-10 | 2017-05-18 | 郝东辉 | Acid purifier |
| CN105233897B (en) * | 2015-11-10 | 2017-06-20 | 郝东辉 | The built-in sour purifier of temperature sensor |
| CN105692554A (en) * | 2016-01-18 | 2016-06-22 | 广西柳化氯碱有限公司 | Method and equipment for producing high-concentration anhydrous hydrogen chloride methanol solution |
| CN106220548A (en) * | 2016-08-31 | 2016-12-14 | 烟台国邦化工机械科技有限公司 | A kind of by rectification take off amine, dehydration obtain high-purity N methyl pyrrolidone method |
| CN109553070A (en) * | 2018-12-17 | 2019-04-02 | 江苏诺斯特拉环保科技有限公司 | Waste hydrochloric acid recycles method of disposal |
| CN111422833A (en) * | 2020-03-20 | 2020-07-17 | 安徽相邦化工有限公司 | Method for preparing ultra-clean high-purity hydrochloric acid by separating hydrogen chloride from hydrochloric acid-containing mother liquor |
| CN111879888A (en) * | 2020-08-03 | 2020-11-03 | 江苏三美化工有限公司 | Method for detecting fluoride ions in hydrochloric acid |
| CN112062089A (en) * | 2020-08-27 | 2020-12-11 | 福建天甫电子材料有限公司 | Preparation process of electronic grade hydrochloric acid |
| WO2022241690A1 (en) * | 2021-05-19 | 2022-11-24 | Dow Global Technologies Llc | Processes for purifying organic amines |
| CN113401872B (en) * | 2021-06-10 | 2023-03-24 | 江阴润玛电子材料股份有限公司 | Production process of hydrochloric acid for integrated circuit |
| CN113307228B (en) * | 2021-07-08 | 2022-11-18 | 华融化学股份有限公司 | Production method of electronic grade hydrochloric acid |
| CN113620249B (en) * | 2021-08-04 | 2023-02-28 | 河北卓泰肥业有限公司 | Method and system for producing reagent hydrochloric acid by using Mannheim furnace tail gas |
| CN114042432B (en) * | 2021-11-05 | 2023-04-11 | 临海市利民化工有限公司 | Rectifying tower filler for dry separation of hydrogen chloride and preparation method thereof |
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